Stabilization of silver halide emulsions

Description

[0001] This invention relates to silver halide photographic emulsions and particularly to the stabilization of silver halide photographic emulsions against increased speed and lost contrast with aging.

[0002] Silver halide is naturally sensitive to only limited portions of the electromagnetic spectrum and its sensitivity within that limited range is low. It is conventional in the photographic art to broaden the range of sensitivity by spectral sensitization of the silver halide grains using sensitizing dyes. It is also conventional to increase the sensitivity of the grains themselves by treating them chemically during growth or ripening or after formation. Chemical sensitization is traditionally performed with sulfur sensitizers (particularly thiosulfate) and gold compounds.

[0003] The compounds used in chemically sensitizing silver halide or their by-products remain in the silver halide emulsion or on the silver halide grains after chemcial sensitization has been completed. This along with other materials and physical conditions allows additional changes in sensitivity to occur after formulation of the final silver halide emulsion. Although these changes may include an increase of speed on aging, such changes are undesirable. Users of photographic materials must be assured of photographic properties and particularly the speed and contrast of the material in order to properly use the photographic element. Uncontrolled increases in speed would lead to overexposure of film by users if subtle alterations in exposure were not made by the photographer. It would be far better if the speed of photographic films could be stabilized against changes with aging.

[0004] Many different classes of materials have been added to silver halide emulsions to alter their properties and to stabilize the properties thus obtained.

[0005] Amongst the many materials used in the preparation of silver halide grains are rhodium salts which are present during precipitation to increase the contrast of the emulsion. Both U.S. Patent Nos. 3,720,516 and 3,982,948 teach the use of rhodium salts in precipitation of silver halide grains and the use of stabilizing compounds in the emulsion preparation or prior to ripening.

[0006] Amongst those materials used to stabilize silver halide emulsions, uracils (including within that generic term thiouracils) have been taught as stabilizers (e.g., U.S. Patent Nos. 2,231,127; 2,232,707; 2,319,090; 3,622,340; 3,692,527; 3,837,857 and 3,982,948), as have metal salts such as cadmium bromide (U.S. Patent No. 3,488,709), manganous salts (U.S. Patent No. 3,720,516 and Canadian Patent No. 976,411), hydroxy- triazaindolizines (U.S. Patent No. 2,444,605) nitroso derivatives of phenols (U.S. Patent No. 3,725,077), cobalt and manganese chelates (U.S. Patent No. 3,556,797), decomposition products of nucleic acids (U.S. Patent No. 3,982,948) and many other materials. Each of these materials tend to have some beneficial effect in stabilizing silver halide, but only to a limited degree.

[0007] Antifoggants are also generally used in photographic emulsions to prevent the formation of spurious development sites on silver halide grains. The art teaches many different types of compounds as antifoggants, including the oxime derivatives of British Patent No. 623,448 the phenol derivatives (including aldoximes) of British Patent No. 988,052 and the fused cyclic structures of U.S. Patent No. 2,566,659.

[0008] As previously mentioned, it is common practice to broaden the range of sensitivity by spectral sensitization of the silver halide grains using sensitizing dyes. The combination of sensitizing dyes (particularly the cyanine dyes which are the dyes of choice in the art) with silver halide emulsions, the grains of which were precipitated in the presence of rhodium salts, causes a particularly adverse effect. The combination of the dye and rhodium doped grains causes an increase in instability in the emulsion. The emulsion more rapidly increases its speed and loses contrast. This creates a serious problem in attempting to combine rhodium doped silver halide grains and merocyanine sensitizing dyes.

[0009] It has been found that the combination of uracils or thiouracils with particular substituted phenols provides a particularly useful stabilizing system for photographic silver halide emulsions. THe effect of this combination of components is unexpected and could not be anticipated from the behaviour of the individual components in photographic silver halide emulsions.

[0010] Therefore according to the present invention there is provided a photographic silver halide emulsion in hydrophilic binder having therein from 0.05 mg to 12 of a stabilizing system per gram mol of silver halide characterized in that the stabilizing system comprises the combination of from 5 to 95 percent by weight of a substituted phenol of the formula:

in which R' is selected from aldoxime, amide, anilide, and ester,

R² and R³ are independently selected from hydrogen, hydroxy, alkoxy or 1 to 12 carbon atoms and alkyl of 1 to 12 carbon atoms, with at least one of R² and R³ being hydrogen or together R² and R³ form a fused-on benzene ring.

[0011] Photographic emulsions according to the invention can be stabilized against speed variations with aging by combining a) lithium salts, b) manganous salts, c) pyrimidine stabilizers, d) uracils or thiouracils and e) the derivatives of phenols defined above. This stabilizer combination is particularly desirable in rhodium doped silver halide emulsions and most particularly in such emulsions sensitized with dyes, and particularly merocyanine sensitizing dyes. Such emulsions are particularly desirable as rapid access developable graphic arts photographic materials. The combination of classes of 1) uracils or thiouracils and 2) the phenol derivatives by themselves show a synergistic effect. That effect is even better in combination with the other three classes of materials used as stabilizers.

[0012] The stabilizer system of at least two and preferably five ingredients used according to the present invention are generally added to the light-sensitive silver halide emulsion after ripening. They may be added directly to the emulsion or, in part or in whole, provided to the emulsion from other layers within the photographic element. The concentration of the total amount of the stabilizer system may be varied within broad limits, with stabilization noted with 0.05 mg to 12 g of stabilizer system to each gram mole of silver halide. Preferably between 0.1 and 10 g of stabilizer system per mole of silver halide is used.

[0013] The stabilizers according to the invention may be used in any silver halide emulsion. Suitable silver halides are silver chloride, silver bromide, silver chlorobromide or mixtures thereof, optionally with a small silver iodide content of up to 10 mole percent. The silver halide is generally coated at 1.5 to 10 g/m², preferably 2.5 g/m² and most preferably 3-5 g/m² on a substrate. Narrow grain sizes with an average diameter between 0.1 -0.8 microns, preferably between 0.15 and 0.5 and most preferably between 0.20 and 0.30 microns are generally used. The silver halides may be dispersed on the usual hydrophilic compounds, for example, carboxymethyl-cellulose, alkyl cellulose, hydroxyethylcellulose, starch or its derivatives, carrageenates, polyvinyl alcohol, polyvinylpyrrolidone, alginic acid and its salts, ester or amides, and preferably gelatin. Such emulsions are particularly desirable as graphic arts photographic materials.

[0014] The combinations of the classes of 1) uracils (including thiouracils) and 2) the phenol derivatives by themselves show a synergistic effect. That effect is even better in combination with the other three classes of materials used as stabilizers.

[0015] The emulsions may be chemically sensitized in the usual manner, for example, with salts of noble metals such as gold, ruthenium, rhodium, palladium, iridium or platinum. Sensitization with gold salts is described in the article by R. Koslowsky, Z. Wiss. Phot. 46, 65-72 (1951).

[0016] The emulsions may also be chemically sensitized e.g. by the addition of compounds which contain sulfur during chemical ripening, for example, allylisothiocyanate, allyl thiourea, sodium thiosulfate or the like. Reducing agents, e.g. the tin compounds described in Belgian Patent Nos. 493,464 and 568,687, or polyamines such as diethylene triamine or aminomethylsulfinic acid derivatives, e.g. those mentioned in Belgian Patent No. 547,323, may also be used as chemical sensitizers.

[0017] The emulsions may also be sensitized with polyalkylene oxide derivatives, e.g. with polyethylene oxide having a molecular weight of between 1000 and 20,000, with condensation products of alkylene oxides and aliphatic alcohols or glycols or cyclic dehydration products of hexitols, or with alkyl substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides. The condensation products have a molecular weight of at least 700 and preferably more than 1000. These sensitizers may, of course, also be combined in order to achieve special effects, as described in Belgian Patent No. 537,278 and in British Patent No. 727,982. The use of polyalkylene oxides in amounts of 0.1 to 2 grams per mole of silver is particularly desirable to enable lithographic processing.

[0018] The emulsions may also be optically sensitized, e.g. with the usual polymethine dyes such as neutro- cyanines, cyanines, merocyanines, basic or acid carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonoles and the like. Sensitizers of this type have been described in the work by F. M. Hamer "The Cyanine Dyes and Related Compounds" (1964).

[0019] Merocyanine dyes are well known in the photographic art as spectral sensitizing dyes. General teachings of these dyes include U.S. Patent 2,493,748, "Merocyanines", L.G.S. Brooker et al. J.A.C.S., 73 5326-5332 (1951) and L.G.S. Brooker et al J.A.C.S., 73 5332-50 (1951). A general representative formula of such sensitizing merocyanine dyes is:

wherein R" and R^b independently represent a member selected from the group consisting of an alcohol radical and an aryl group (preferably phenyl or substituted phenyl), L represents a methine group, n is 1 or 2, m is 1, or 3, d is 1, or 3, Q represents the non-metallic atoms (preferably C, S, Se, N and 0) necessary to complete a 5-, 6-, or 7-membered heterocyclic nucleus (which may be substituted as with a sulfonalkyl or carboxyalkyl group) which may be present in a metal or ammonium salt form of the heterocyclic nucleus, Q' being selected from the group of oxygen, sulfur and

wherein R° is selected from the group consisting of an alcohol radical and an aryl group, and Z represents the non-metallic atoms (preferably selected from C, N, Se, S or 0) to complete a 5- or 6-membered heterocyclic nucleus. "Simple" and generally preferred merocyanines have the above structure where d = 1. Preferred merocyanines for the present invention have the structure

wherein R^e is alkyl of up to 12 carbon atoms, preferably 2 to 8 carbon atoms and most preferably ethyl,

R^f is aryl of 6 to 10 carbon atoms, sulfoalkyl or carboxyalkyl of 1 to 12 carbon atoms in the alkyl, preferably phenyl or 1 to 8 carbon atoms in the alkyl, and most preferably phenyl or CH₂COOH, and

R⁹ is aryl of 6 to 10 carbon atoms or alkyl of 1 to 12 carbon atoms, preferably phenyl or alkyl of 2 to 8 carbon atoms, and most preferably phenyl or ethyl.

[0020] Substitution of the benzene ring with common substituents such as alkyl, alkoxy, halogen, aryl and the like are of course allowable and anticipated in the practice of the present invention.

[0021] The emulsions may be hardened in the usual manner, for example, with formaldehyde of halosubstituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters, dialdehydes and the like.

[0022] The silver halide emulsions according to the invention may contain other stabilizers in addition to those described above, preferably tetra-or penta-azaindenes and especially those which are substituted with hydroxyl or amino groups. Compounds of this type have been described in the article by Birr in "Zeitschrift fur Wissenschaftlich Photographic," volume 47, 1952, page 2 to 28. The emulsions may also contain heterocyclic mercapto compounds such as mercapto tetrazoles or mercury compounds as stabilizers.

[0023] The minimum stabilizing system according to the present invention comprises from 5 to 95% by weight of a uracil (including the thiouracils also known as the 2-mercapto-4-hydroxy-pyrimidines) and from 95 to 5% by weight of a phenol derivative having the formula

in which R' is selected from: aldoxime, amides e.g.,

in which R⁴ and R⁵ are selected from hydrogen, alkyl of 1 to 12 carbon atoms preferably of 1 to 4 carbon atoms, and phenyl with no more than one of R⁴ and R⁵ being phenyl, anilide, or ester e.g. -COOR⁶, in which R⁶ is selected from alkyl of 1 to 12 carbon atoms, phenyl, or alkylphenyl of no more than 12 carbon atoms, preferably with no more than 4 carbon atoms, in the alkyl of the alkylphenyl,

R² and R³ are selected from hydrogen, hydroxy, alkoxy of 1 to 12 carbon atoms, or alkyl of 1 to 12 carbon atoms, or maybe the atoms necessary to form a fused-on benzene ring with at least one of R² and R³ being hydrogen. Preferably, R' is aldoxime and both R² and R³ are hydrogen or alkyl of 1 to 4 carbon atoms most preferably both R² and R³ are hydrogen (hereinafter this most preferred phenol will be referred to as SCA for salicylaldoxime).

[0024] The preferred uracils are the 2-mercapto-4-hydroxy-pyrimidines and especially the 2-mercapto-4-hydroxy-6-alkyl-pyrimidines (with the alkyl groups 1 to 20, preferably 1 to 12 and most preferably 1 to 4 carbon atoms).

[0025] The stabilizer system of the present invention may further comprise up to 50 percent by weight of manganous salts (preferably 5 to 45%), up to 45 percent by weight water soluble lithium salt (preferably 5 to 40%), and upto 15 percent by weight of pyrimidine stabilizers (preferably 0.5 to 10%). Other stabilizers known in the art may, of course, be added to the emulsion. The lithium and manganous salts may, for example, be nitrate, sulfate, or halide (e.g., bromide and chloride) salts. Any water-soluble inorganic salt of lithium and manganese (II) are particularly useful. The pyrimidine compounds are particularly useful. The pyrimidine compounds particularly useful in the present invention are preferably triazolopyrimidines and maybe represented by the formula :

Wherein R⁷ is selected from hydrogen, alkyl, alkaryl, aryl, alicyclic or heterocylic (preferably each of which has no more than 12 carbon atoms and where the heterocyclic is comprised of only, C, S, N and 0 atoms, The alkyl groups are more preferably 1 to 4 carbon atoms),

R⁸ is selected from alkyl, aralkyl, aryl, alicyclic, heterocyclic, hydroxy, amino or carbylalkoxy (preferably with up to 12 carbon atoms and where the heterocyclic is comprised of only C, S, N and O atoms. The alkyl groups are most preferably 1 to 4 carbon atoms), and

R⁹ is selected from hydrogen, alkyl and aralkyl of up to 12 carbon atoms, preferably 1 to 4 carbon atoms in the alkyl.

R⁷ and R⁸ may also represent the atoms necessary to form a fused-on benzene ring. Preferably, R⁷ is hydrogen or alkyl of 1 to 4 carbon atoms, R⁸ is hydrogen or alkyl of 1 to 4 carbon atoms and R⁹ is hydrogen or alkyl of 1 to 4 carbon atoms. Most preferably, R⁷ is hydrogen and R⁸ and R⁹ are methyl. This most preferred pyrimidine is hereinafter referred to as MPP.

[0026] Any substrate may be used in the practice of the invention. Conventional substrates such as polymeric film (e.g., polyester, cellulose acetate and the like), paper, etc. may be used.

[0027] Rapid access development chemistry usually comprises high sulfite content hydroquinone developer solutions which are aerially stable and are often capable of producing high contrast images. Metol or phenidone are usually included in the solution.

[0028] Practice of the present invention will be further illustrated by the following Examples. In all Examples, a standard rapid access processable negative film was prepared on polyester. The emulsion comprised a 64/ 36 chlorobromide emulsion doped with rhodium according to conventional precipitation techniques. The emulsion was also conventionally chemically sensitized with thiosulfate and cold and spectrally sensitized with a merocyanine sensitizing dye. All emulsions were also stabilized with 8 ml/mol (of silver halide) of a 5 Molar aqueous solution of lithium nitrate, and 12 ml/mol of a 1.5 molar aqueous solution of manganous nitrate. All emulsions were coated, sensitometrically exposed and rapid access processed for 20 seconds at (106°F) in a commercially available 3M RA-24 processor with the chemistry described in "Photographic Processing Chemistry", L.F.A. Mason, Wiley Press, 1975, p. 142 as the D62 developer. (3M is a registered Trade Mark).

Examples

[0029] The following stabilizers were added to the standard emulsion in various amounts, potassium bromide, 6-methyl-2-thiouracil (hereinafter MTU), and salicylaldoxime (hereinafter SCA). One portion of each photographic element was immediately exposed and developed while a second portion was incubated for sixty hours at 60°C in a sealed bag. The second portion was then exposed and developed in an identical manner. Measurements were taken of the speed and the contrast (OC is overall contrast, OA is toe contrast). Speed is recorded as the relative log of the reciprocal exposure at the point where density is 0.2 above D_min. Contrast is the slope of the D vs LogE curve take between 0.5 and 2.5 density above D_min. Toe contrast is the slope between 0.07 and 0.17 above D_min. The change in speed (A Speed) and change in contrast (AOC or Δ⊖A) were readily determined by subtracting the initial value from the value after incubation. The data were as follows:

[0030] In the next five examples, all samples also contained 12 ml per mole of silver halide of a one molar aqueous solution of KBr.

[0031] Several observations are apparent: There is both some gain in contrast and actual loss of speed with higher concentrations of 6-methyl-2-thiouracil. Neither 6-methyl-2-thiouracil nor salicylaldoxime show significant speed loss stabilization properties by themselves, although some minor effects were noted in Examples 3 and 4. The combination of the uracil and the substituted phenol (the salicylaldoxime) showed a dramatic reduction in speed gain on incubation. This is particularly surprising in view of the fact that the substituted phenols are thought to be only antifoggants (e.g., U.K. Patent No. 988,052) and are not taught as stabilizers. Furthermore, not only is the speed increase reduced, but the contrast loss is also diminished by the combination of the uracil and the nitroso-substituted phenol. Although these additives cause some initial loss of speed in the emulsion, the ordinarily skilled photographic and emulsion chemist could regain that lost speed by known adjustments in the properties and characteristics of the silver halide grains, such as their size.

[0032] The most preferred compositions for maximizing speed and contrast with minimum speed gain and contrast loss with the standard emulsion used in the examples of the present invention were found to contain approximately 8 ml/M 5M LiN0₃, 12 ml/M 1.5 M Mn(N0₃)₂, 20 ml/M 1% MPP, 12 ml/M 10% salicylaldoxime, 12 ml/M 1 M KBr, and 300 to 400 mg/M MTU. The data for such compositions appears below:

Claims

1. A photographic silver halide emulsion in hydrophilic binder having therein from 0.05 mg to 12 g of a stabilizing system per gram mol of silver halide characterised in that the stabilizing system comprises the combination of from 5 to 95 percent by weight of a uracil or thiouracil and from 95 to 5 percent by weight of a substituted phenol of the formula:

in which R' is selected from aldoxime, amide, anilide, and ester,

R² and R³ are independently selected from hydrogen, hydroxy, alkoxy of 1 to 12 carbon atoms and alkyl of 1 to 12 carbon atoms, with at least one of R² and R³ being hydrogen or together R² and R³ form a fused-on benzene ring.

2. An emulsion as claimed in Claim 1 characterized in that R¹ is selected from

in which R⁴ and R⁵ are independently selected from hydrogen, alkyl of 1 to 12 carbon atoms, and phenyl, with no more than one of R⁴ and R⁵ being phenyl, and R⁶ is selected from alkyl of 1 to 12 carbon atoms, phenyl, or alkylphenyl of no more tha 12 carbon atoms, and

R² and R³ are selected from hydrogen and alkyl of 1 to 12 carbon atoms.

3. An emulsion as claimed in Claim 1 or Claim 2 characterised in that the silver halide grains are doped with rhodium.

4. An emulsion as claimed in any preceding claim characterised in that the substituted phenol is an aldoxime of the formula:

in which R² and R³ are selected from hydrogen and alkyl of 1 to 4 carbon atoms.

5. An emulsion as claimed in any preceding claim characterised in that the uracil is a 2-mercapto-4-hydroxy-pyrimidine.

6. An emulsion as claimed in any preceding claims characterised in that the stabilizing system additionally comprises one or more of water soluble lithium salt stabilizers in an amount up to 45 percent by weight, manganous salt stabilizers in an amount of up to 50 percent by weight, and triazolopyrimidines in an amount up to 15 percent by weight.

7. An emulsion as claimed in any preceding claim wherein a spectrally sensitizing amount of a merocyanine dye is also present in the emulsion.

8. A substrate being a photographic silver halide emulsion as claimed in any preceding claim.

Ansprüche

1. Photographische Silberhalogenid-Emulsion in einem hydrophilen Bindemittel, enthaltend 0,05 mg bis 12 g eines Stabilisatorsystems pro Gramm-Mol Siberhalogenid, dadurch gekennzeichnet, daß das Stabilisatorsystem eine Kombination aus 5 bis 95 Gewichtsprozent eines Uracils oder Thiouracils und 95 bis 5 Gewichtsprozent eines substituierten Phenols der folgenden allgemeinen Formel enthält:

in der R' einen Aldoxim-, einen Amid-, einen Anilid- oder einen Esterrest bedeutet, R² und R³ unabhängig voneinander ein Wasserstoffatom, eine Hydroxylgruppe, einen Alkoxyrest mit 1 bis 12 Kohlenstoffatomen oder einen Alkylrest mit 1 bis 12 Kohlenstoffatomen darstellen, wobei mindestens einer der Reste R² und R³ ein Wasserstoffatom ist oder die Reste R² und R³ zusammen einen ankondensierten Benzolring bilden.

2. Emulsion nach Anspruch 1, dadurch gekennzeichnet, daß R¹

ist, wobei R⁴ und R⁵ unabhängig voneinander ein Wasserstoffatom, einen Alkylrest mit 1 bis 12 Kohlenstoffatomen oder eine Phenylgruppe bedeuten, wobei höchstens einer der Reste R⁴ und R⁵ eine Phenylgruppe ist, und R⁶ einen Alkylrest mit 1 bis 12 Kohlenstoffatomen, eine Phenylgruppe oder einen Alkylphenylrest mit höchstens 12 Kohlenstoffatomen bedeutet, und R² und R³ ein Wasserstoffatom oder einen Alkylrest mit 1 bis 12 Kohlenstoffatomen darstellen.

3. Emulsion nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Silberhalogenidkörner mit Rhodium dotiert sind.

4. Emulsion nach jedem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß das substituierte Phenol ein Aldoxim mit der folgenden allgemeinen Formel ist:

in der R² und R³ ein Wasserstoffatom oder einen Alkylrest mit 1 bis 4 Kohlenstoffatomen bedeuten.

5. Emulsion nach jedem der voragehenden Ansprüche, dadurch gekennzeichnet, daß das Uracil ein 2-Mercapto-4-hydroxyl-pyrimidin ist.

6. Emulsion nach jedem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß das Stabilisatorsystem zusätzlich einen oder mehrere wasserlösliche Lithiumsalzstabilisatbren in einer Menge von bis zu 40 Gewichtsprozent, Mangansalzstabilisatoren in einer Menge von bis zu 50 Gewichtsprozent und Triazolpyrimidine in einer Menge bis zu 15 Gewichtsprozent enthält.

7. Emulsion nach jedem der vorangehenden Ansprüche, wobei auch eine spektralempfindliche Menge eines Merocyaninfarbstoffes in der Emulsion vorhanden ist.

8. Substrat, bestehend aus einer photographischen Silber halogenid-Emulsion nach jedem der vorangehenden Ansprüche.

Revendications

1. Emulsion photographique d'halogénure d'argent dans un liant hydrophile contenant de 0,05 mg à 12 g d'un système stabilisant par molécule-gramme d'halogénure d'argent, caractérisée en ce que le système stabilisant comprend la combinaison de 5 à 95 % en poids d'un uracile ou d'unthiouracile et de 95 à 5 % en poids d'u phénol substitué de formule:

dans laquelle, R¹ est choisi parmi les aldoxime, amide, anilide et ester,

R² et R³ sont choisis indépendamment parmi H, OH, alcoxy en C_1-12 et alkyle en C_1-12, un au moins des R² et R³ étant H, R² et R³ pouvant former ensemble un cycle benzène condensé.

2. Emulsion selon la revendication 1, caractérisée en ce que R¹ est choisi parmi

où R⁴ et R⁵ sont indépendamment choisis parmi H, alkyle en C₁―C₁₂ et phényle, pas plus d'un des R⁴ et R⁵ étant un phényle, et R⁶ est choisi parmi les alkyle en C₁―C₁₂, un phényle ou alkylphényle n'ayant pas plus de 12 atomes de carbone et R² et R³ sont choisis parmi H et alkyle en C₁―C₁₂.

3. Emulsion selon la revendication 1 ou la revendication 2, caractérisée en ce que les grains d'halogénure d'argent sont dopés avec du rhodium.

4. Emulsion selon l'une quelconque des revendications précédéntes, caractérisée en ce que le phénol substitué est un aldoxime de formule:

dans laquelle R² et R³ sont choisis parmi les H et alkyle en C_l-C₄.

5. Emulsion selon l'une quelconque des revendications précédentes, caractérisée en ce que l'uracile est une 2-mercapto-4-hydroxypyrimidine.

6. Emulsion selon l'une quelconque des revendications précédentes, caractérisée en ce que le système stabilisant comprend de plus un ou plusieurs sels de lithium stabilisants solubles dans l'eau en une quantité d'au plus 40 % en poids, des sels manganeux stabilisants en une quantité d'au plus 50 % en poids et des triazolopyrimidines en une quantité d'au plus 15 % en poids.

7. Emulsions selon l'une quelconque des revendications précédentes, dans laquelle un quantité produisant une sensibilisation spectrale d'un colorant de mérocyanine est également présente dans l'émulsion.

8. Substrat muni d'une émulsion photographique d'halogénure d'argent comme revendiqué dans l'une quelconque des revendications précédentes.